Petroleum resins



2,798,865 PETROLEUM RESINS Fred W. Banes, Westfield, Joseph F. Nelson, Rahway, and Robert G. Hoyt, Cranford, N. J., assignors toEsso Research and Engineering Company, a corporation of Delaware i No Drawing. Serial No. 318,068

4 Claims. (Cl. 260-82) Application October 31, 1952,

This invention is concerned with the preparation of high quality, light colored resins from selected steam cracked petroleum fractions and, 'more specifically, with the useof dimers and codimers of cyclopentadienes in conjunction with steam cracked, unsaturated petroleum fractions as feed for preparing polymerized resins with Friedel-Crafts catalysts.

It is known to prepare resins from steam cracked petroleum distillate fractions by polymerization with Friecarbonieed The amount of cyclopentadiene dimers to del-Crafts catalysts. Generally, the cyclodienes, such as cyclopentadiene and methyl cyclopentadiene, if present ice merization conversion levels of 20 to 35% based on the original naphtha feed.

Generally, in the preparation of these petroleum resins, catalyst concentrations of 0.5 up to 3.0% are advantageously employed and the polymerizations are carried out at temperatures of 20 up to 90 C., preferably to 75 C. 4

During the usual process of recovering the cyclodienes from the steam cracked naphthas, both the cyclo and methyl cyclopentadienes are converted to the dimers or .mixed dimers as the result ofthermal dimerization. If

desired, these dimers can be separated and depolymerized and fractionated to give the individual cyclodiene monomers as chemically pure compounds which can be utilized as such.

By operating according to this invention, resins of higher softening points and good qualities can be prepared by including in the unsaturated stream above 5% up to 50%, and preferably from above 5% to of dicyclopentadiene, di-methyl-cyclopentadiene, or di-Crcyclopentadienes, codimers, mixtures of dimers, or concentrates thereof, based on the amount of total hydrobe' added will depend upon two factors, namely, the

in the feed streams, are removed from the steam cracked 1 distillate streams prior to subjecting them to polymerization. It has been discovered that, in producing resins amount of such dimers already present in the feed, and

the final amount required to be present in the polymeri- .zation feed.

from unsaturated, steam cracked petroleum streams,

much better results are obtained when dimers, includfeed in controlled proportions.

ing codimers of the cyclopentadienes are present in the The inclusions of at least one and possibly more, of these materials in the ole- 5' finic feed for preparing the resins permits the Friedel- Crafts polymerization to proceed smoothly, giving a higher yield of resin of a given quality or an equivalent yield 1 of resin of superior quality. The addition of these materials is of particular importance in that they permit the making of resins having appreciably higher softening points.

In carrying out the invention,

ence of steam at temperatures above 1000 F. and up to 1500 F. to give highly unsaturated product streams. The distillate streams having olefinic components boiling in the range of 20 up to about 240 C. largely 20 i It isnecessary to have the cyclodienes present as the dlll'ldlS rather than as the monomers, since the monomers when present in any appreciable concentration in the polymerization reaction mixture, tend to give products having appreciable quantities of insoluble, gelled polymer.

However, the use of the dimers or codimers of cyclopentadiene and methyl cyclopentadiene or concentrates and mixtures thereof, produces completely soluble resinous products as well as the desired resins of increased softening point.

It is contemplated that the unsaturated feed mixtures for the resin process can be obtained in a number of 40 petroleum fractions such as kerosene, gas oil, naphtha, etc. are cracked in the presto 130 C. are then subjected to operations of thermalsoaking and distillation to remove unsaturatedshydrocarbons such as the cyclic diolefins, including cyclopentadiene and methylcyclopentadiene. The material boiling substantially above +130 C. in the initial stream largely consists of previously formed dimers and .codimers of the ways. For instance, the appropriate distillate streams .which arenormally obtained, contain appreciable quantities of the cyclodiene monomers or monomer-dimer mixtures.

Such streams are subjected to thermal soaking for 4 to 8 hours at temperatures of from 100 to 150 C. in order to convert all monomers to the dimers or codimers. The resulting stream is then treated with aluminumchloride or some other Friedel-Crafts catalyst in order to produce the improved resinous products. It may be necessary to adjust the concentration of dimers by the addition of more dimers in order to have the desired concentration in the polymerization feed.

cyclopentadienes. The resulting naphtha stream of boil-- ing range 20 to 130 C. usually contains about 14 to 30% benzene, 4 to9% toluene, 7 to 22% diolefins, 0 to 5% paraffins and from 34 to 75% olefins and cyclic olefins. The diolefincontent of the mixture was obtained by reacting a mixture of 1.5 to 3.0 ml. of sample and 2.5 ml. of chloromaleic anhydride (diluted with 2 ml. benzene containing 0.1% tertiary butyl catechol) for 3 As an alternate method, the cyclodienes can be converted to dimers by thermal soaking, following which the total stream is subjected to distillation under conditions ,1 wherebyjthe cyclodiene dimers are maintained in the -dimerizedform, and are separated as a residue. The

the individual cyclodiene monomers.

dimers are then depolymerized and fractionated to give If desired, selective "portions of the cyclodienes are dimerized and added to hours at 100 C., and steam distilling the resulting re- 3 action mixture for 2 hours to recover HCl (1 mole/ mole of dio lefin). When these fractions of steam cracked distillate are treated with a catalyst such as aluminum chloride, aluminum bromide, and the like, about 10% up to 40% of the unsaturated naphtha is converted to polymeric materials. 'In general, these resins are found to be somewhat brittle, and the softening points of these materials are too low for example, inmaking up floor tile and certain coatings.

As a typical example, the aluminum chlorideresin products have softening points of 75 to 90 C. at polyto permit them to be used as such,

the separated distillate fraction in order to obtain the improved olefinic feed for the polymerization.

Another method utilizes a recycle stream from the recovery of the cyclodienes. During the recovery of cyclopentadiene and methyl cyclopentadiene from the dimer concentrates after thermal soaking, a product fractionator bottoms is normally obtained which contains unrecovered cyclodiolefin dimers as well as C8 to C10 aromatics and C9 to C11 olefins and diolefins. If this bottoms stream is taken as a purge stream and added to the unsaturated naphtha from which the cyclodienes have been removed, the resulting mixture is found to be an,

t excellent feedstock for producing higher softening point resinsby Friedel-Crafts polymerization.

In addition to the improved softening points and solubilities of the resins prepared according to the invention, it has been furtherfoundthat'the product's have greater usefulness since they can be thermally bodied toiproduce resins having even highersoftening points. Ontheother hand, it has beenfound that similar'resin's prepared from feed stock in which no cyclopentadienes or their dimers were present, harden more slowly and darken severely during the attempted thermal bodying process.

his to be understoodthatthisimproved method for preparingnresin's can be satisfactorily'operatedeither asa batch or continuous process.

Typical examples'of'the'invention are set forth below, although it is not intended'to' limitthe invention in' any way to the particular experiments presented."

products had the desirable higher softening pointsabove about 90 C. and the color of theresins was as'goodor better than the control. In every case'when 5% ormore of the dimer stream was added, the yield of resins was higher and the softening point was 10 to higherthan that of the control. In addition, Iruns 1-6, inclusive, produced a completely soluble resin having no gel content. However, in runs7 and 8 Wherecyclodiene monomers were added to the naphtha stream, undesirable amounts of insoluble gel were formed.

Table I COMPOSITION OF CYOLODIENEAND NAPHTHA STREAMS USED IN PREPARING FEED Naphtha Streems-Desiguation Distillation, Wt. Percent 13 Composition, Wt. Percent:

Aromatics Benzene Toluene.

HCADMN enormou Cyclopentadlene Streams-Designation;

00111 osition, Wt. Percent:

yclopentadiene Methylcyciopentadiene- O Cyclopentadienes; Acyclic Cs dienes- Other Hydrocarbons l Dimers or codimers. lncludlng-dimerized dloleflns. Monomers.

Table II Hydrocarbon Feed Resin- Resln Properties -Yleid Run No. I

Naphtha Weight Oyelo- Weight Weight Soft.1?t.',!

Stream Percent I diene Percent Percent" O. Color- Stream on"Feed" A 100 78 I 3: A 98. p d 2 28.3 89. 3-- A 95' c 5 32 901 4 A r c 10 34' 93': i 2. A 90 d 10 34 r 97 2 A 90 a 10 34.6" 90 j 3 A- 90 e. 10.. 36'; 96' 3 A. 90v f 10 34. 6. 3

1 Includes cross-linked, insoluble gel polymer.

Gel was also deposited 0n-.reactor walls.

9 Color of a solution of 1 g; resin in 67 ml. of xylenes compared to the Gardner Color Index. 3 Batch polymerizatlons. Rlng'and ball softening point (ASTM E28-51T)- EXAMPLE 1 EXAMPLEZ Alsecond series of'resins was prepared usingnaphtha' B" of 'Table I in combination with varying amountsof cyclodiene dimer concentrates a and b. The'data'are shown in Table III. The addition ofthedimer concentratein each case resulted in outstanding increases in resin soften ingepoint.

Table III I Hydrocarbon Feed (Table I) Wt. percent on Resin Proper- Feed ties Run Percent No. Naphtha Wt. Oyclo- Wt. A101 1 Stream Perdieno Per- Resin 1 Liquid Soft. Iodine cent Stream cent Polymer Pt.,0. No.

9 B 100 1.5 31'. 5 4.7 87 192 10-. B 90 b 10 1.5 34.4 3.2 101 198 l 11..--.. B 80 b 1. 5 34 4 113 160 12. B 90 a 10 1. 5 33 4. 6 102 168 13..-- B a 20 1.5 35.8 6.0 '112 148 1 No gel produced in any of these runs. 1 ASTM (D-555-47).

EXAMPLE 3 thermal treatment to give naphtha E. 'No dimers were separately added. Run 29 uses, as feed, naphtha E to which has been added 10% of mixed cyclodienedimer concentrate.

It is seen from the data of whether the dimers are prepared by dimerizing in situ the cyclodienes initially present in the naphtha stream, '01" whether the dimers or dimer concentrate are added to the naphtha stream in a separate step, the resin production is entirely satisfactory. In both runs 28 and 29, the yield of resin was high, the amount of liquid polymer was low Table IV Hydrocarbon Feed (TableI) Weightgercent Resin Properties on cc i Per- RnnNo. cent 1 l Naphtha Wt. Cyclo- Wt A101 3 Resin Liquid Soft. Color Iodine Stream Perdiene Per- Polymer Pt.,O. Index Number cent Stream cent l C c 10 1.0 24.4 4. 6 91 5 214.8 C 90 c 10 2.0 24. 6 5. 5 95 7 203. 0 C 90 d 10 1.0 24. 0 3. 5 108. 5 6 238. l C 90 d 10 2.0 28.0 4. 6 112 8 218. 3 A 90 a 10 2. 0 25. 4 4. 6 103 6 210.0 B 1.0 81. 5 4. 7 B7 3 192 B 100 2.0 33. 0 5.0 92 5 B 90 d 10 1.0 35. 3 5.0 115 4 196. 3 B 90 d 10 2. 0 39. 3 3. 5 116 6 B 80 d 20 1.0 39.9 3. 9 128 4. 5 B 80 d 20 2.0 40. 8 6.3 130 7.0 215. 6

EXAMPLE 4 This example shows that the cyclodiene dimers may be present in the feed and need merely be controlled in order and superior high softening point resins were obtained. The poiymerizations were carried out at 45 C. using 0.75% AlCls.

Table V Hydrocarbon Feed (Table I) Wt. Percent on Wt. Per- Feed Resin cent of Soft. Run No. Dimcrs Point,

Naphtha Wt. Cyolo- Wt. in Liquid 0.

Stream Perdiene Per- Feed Resin Polyoeut Stream cent mer D 100 1.5 32.2 3.4 90 E 100 9. 7 36. 4 3. 8 98 E 90 a 10 16. 5 37. 2 4. 8 107 to accomplish satisfactory results. In run 27, substan- EXAMPLE 5 tially all cyclodiene dimers had been removed from the feed and none were added. In run 28, the naphtha feed used contained initially mixed cyclodiene monomers and dimers which were converted completely to dimers by The effect of polymerization temperature was also studied. A catalyst of 1.5% AlCls was used. In a series of runs shown in Table VI, it is shown that as the tem- 75 perature increases, the yield of resin increases. For a Table V that regardless. of

given softening point, a higher yield of solid resin is obtained with little increase in the undesirable liquid polymer fraction.

the separated dimerized cyclic diolefins, subjecting said unsaturated mixture to polymerization in the presence of an AlCla catalyst at a reaction temperature between g .gsmmm-tswn.

Whatiscl'aimed is:

11A process for the preparation of petroleum resins whichcomprises .the. steps of preparing a steam cracked distillate fractionof boilingrange'30 to 130 C. from whicliisubst'antially all of the cyclodienes have been removed} adding to said fraction from to of.

cyclopentadiene' dimers and polymerizing the resulting miir'ture'with aluminum chloride catalyst at a temperature '2. process for the preparation of petroleum resins which comprises cracking a petroleum fraction at above 1000 F. in the presence of steam to give a cracked product stream, isolating an unsaturated naphtha stream, thermally soaking said stream to' dimerize substantially all cyclic diolefins, separating two fractions therefrom, a cyclic diolefin dimer stream aud a naphtha stream boiling substantially from 20 to. 130 C. and containing from 14 to Weight percent benzene, from 4 to 9 weight percent toluene, from 7 to 22 weight percent diolefins, from 0 to 5 weight percent paraffins, and from 34 to 75 weight percent olefins, adding to said naphtha stream from 5 to 20 weight percent of and C., therefrom.

3; A resin product in claim2.

4. A process for the preparation of petroleum resins which comprises preparinga steam-cracked distillate framtion boiling-between 30'and C.,h'eating said-fractionto dimeri'ze substantiallyall the cyclic diolefins contained' therein and polymerizing the resulting mixture with aluminum chloride catalyst at a temperature 'between- 0 and 70 C.

References Cited in the file of this patent UNITED STATES PATENTS" and separating the I etroleum r resin product prepared by the process described 1 ,982,708 Thomas et all Dec. 4, 1934 2,067,073- Carmody. Jan. 5, 1937 2,352,980 Soday -July'4; 1944 OTHER "REFERENCES Wilson'et' ah: India Rubber World; 110," page's6'163; April 1944i Whitmore: Organic Chemistry, page-63911937 

1. A PROCESS FOR THE PREPARATION OF PETROLEUM RESINS WHICH COMPRISES THE STEPS OF PREPARING A STEAM CRACKED DISTILLATE FRACTION OF BOILING RANGE 30* TO 130*C. FROM WHICH SUBSTANTIALLY ALL OF THE CYCLODIENES HAVE BEEN REMOVED, ADDING TO SAID FRACTION FROM 5% TO 20% OF CYCLOPENTADIENE DIMERS AND POLYMERIZING THE RESULTING MIXTURE WITH ALUMINUM CHLORIDE CATALYST AT A TEMPERATURE OF FROM 0* TO 70*C. 